Treating the hair with oxazoline polymer and copolymer hair dressing formulations

ABSTRACT

AN IMPROVED HAIR DRESSING FORMULATION CONTAINING (A) FROM ABOUT 0.1 TO ABOUT 10 WEIGHT PERCENT OF A WATERDISPERSIBLE POLYMER HAVING A REDUCED VISCOSITY RANGING FROM ABOUT 0.5 TO ABOUT 5.0 AS DETERMINED ON A 0.52 WEIGHT PERCENT SOLUTION OF POLYMER IN META-CRESOL AT25*C., SAID POLYMER BEING SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS AND COPOLYMERS OF MONOMERS OF THE FORMULA:   2-R-4-OXAZOLINE   WHEREIN R IS A SUBSTITUENT SELECTED FROM THE GROUP CONSISTING OF   CH3-, C2H5-, CH3-(CH2)(N-1)-COO-(CH2)M-,   CH3-(CH2)(N-1)-OOC-(CH2)M-   WHEREIN THE SUM OF THE INTEGERS M AND N IS NOT GREATER THAN 6, AND   NC-(CH2)K-, (CH3-)2-N-CO-(CH2)K-   WHEREIN K IS 0 TO 3; AND (B) A CARRIER FOR SAID POLYMER SELECTED FROM THE GROUP CONSISTING OF WATER, ETHANOL, ISOPROPANOL, AND MIXTURES THEREOF.

United States Patent ce Patented May 18, 1971 3,579,630 TREATING THE HAIR WITH OXAZOLINE POLYMER AND COPOLYMER HAIR DRESS- ING FURMULATIONS Jack L. Herz, Parsippany, Alan J. Levy and Morton H. Litt, Morristown, and Joseph L. Zuckerman, Livingston, N.J., assignors to Allied Chemical Corporation, New York, NJY. No Drawing. Filed Dec. 29, 1966, Ser. No. 605,590 Int. Cl. A61]; 7/06 US. Cl. 424-47 9 Claims ABSTRACT OF THE DISCLOSURE wherein the sum of the integers in and n is not greater than 6, and

wherein k is to 3; and (b) a carrier for said polymer selected from the group consisting of water, ethanol, isopropanol, and mixtures thereof.

This invention relates to novel hair dressing formulations, especially hair dressing sprays. More particularly, this invertion relates to hair dressing formulations containing polymers or copolymers derived from a monomer of the. general formula:

wherein R is a substituent selected from the group consisting of churn-n0 -(om)m, oN(oH2 iand (0 a)2 C H2) k wherein k is from 0 to 3 inclusive and wherein the sum of the integers in and n is not greater than 6.

Desirable characteristics of a hair dressing composition are that it form a non-tacky, flexible film on the hair andv that this film have a good memory; i.e. that hair treated with the dressing will return to its original shape, thereby imparting improved curl retention to the hair. It should have good adhesion to the hair and not flake off even when combed. Desirable films Will be clear and bright, odorless and colorless and be readily removable from the hair by shampooing. Additionally, the resin should be soluble in common solvents and, particularly in the case of sprays, the resin should be soluble in the alkanols, and its solutions miscible with common aerosol propellants.

The invention will be described herein mainly with reference to hair spray formulations which is the preferred application, but it will be apparent that the invention contemplates as well usage of the resinous formulations to other hair dressing preparations.

While a number of film-forming resins are currently being widely sold in hair spray formulations, none of them are wholly satisfactory. For example, with some of the resins of the prior art, large amounts of other additives must be added which may add to the cost of the compounded formulation or of themselves impart other disadvantages; e.g., polyvinyl pyrrolidone polymers, because of their relative brittleness, must be plasticized to obtain a commercially satisfactory hair spray resin. Resins comprising vinyl acetate/crotonic acid copolymers must be neutralized before being used as a hair spray. Others such as dirnethyl hydantoin formaldehyde and the acrylic resins have a pungent and unpleasant odor which must be. masked with perfumes to be acceptable. Still others, to be effective, require relatively large amounts of resin.

It is therefore an object of this invention to provide resinous hair dressing compositions which are odorless and which form non-tacky flexible films.

It is another object of this invention to provide superior hair dressing formulations employing certain specified polymers in weight ratios in the formulation which are relatively low.

It is a further object of this invention to provide improved hair spray formulations which impart a high degree of curl retention, and which produce films of excellent sheen, which are non-tacky and easily removable from the hair.

Further objects and advantages will become apparent from the description of the invention which follows in greater detail.

It has now been found in accordance with this invention that excellent hair dressing compositions may be derived from the use of a minor proportion, i.e., about 10% by weight or less, in the hair dressing composition,

of polymers obtained by homopolymerizing or by copolymerizing monomeric compounds of the formula N-CH2 RO\ O-CHi wherein R is a substituent selected from the group consisting of i 3-. 2H5-. OnH2n+1CO(CH of monomeric compounds of the following general formula:

Rr-C o- H, (II) wherein R is a substituent of the formula C H or C H wherein y is from 3 to 21.

The homopolymers of the current invention may be represented by recurring units of the general formula:

and the copolymers by recurring units of the general Preferably a blend of polymers which is water dispersible is employed. Water dispersible, as the term is herein employed, contemplates polymeric compositions which are either water soluble as such or are capable of being rendered water soluble, such as by partial hydrolysis of the polymers, or are easily emulsifiable though not soluble. In general the proportion of monomers in a selected copolymerizable mixture is adjusted depending on the properties of the specific monomers so that a dispersible copolymer is obtained which can readily be rinsed from the hair as by shampooing. Suitable polymeric copolymers may be prepared, for example, by polymerizing a mixture containing from about 50 to about 99.9' mol percent, preferably from about 85 to 99.5 mol percent, of either 2-methyl-2-oxazoline or 2-ethyl-2-oxazoline and from about 50 to about 0.1 mol percent, preferably from about to about 0.5 mol percent, of a comonomer or a mixture of comonomers of Formula II above.

Films obtained from solutions of these resins have excellent curl retention ability, are clear, bright, odorless and flexible, and dry quickly. In addition, the resins have a quality of slip or lubricity which imparts added manageability to the hair and makes the hair easy to comb out. Since the polymers and copolymers of the invention are water dispersible, i.e., water soluble or nearly soluble, they can be removed from the hair readily by shampooing. Because they are also soluble in common organic solvents, e.g., ethanol and isopropanol and are compatible with propellents as well as with perfumes and modifiers, they adapt well for use in hair spray formulations. In addition to their utility in hair spray formulations, these properties are also advantageous in hair set lotions, usually applied to the hair from aqueous or mixed alcohol-water solutions, such as by rubbing in by hand or by comb application.

The polymers and copolymers of the invention may be prepared by polymerizing the monomers or comonomers in a suitable manner. One method involves reacting the monomers in an inert atmosphere in the presence of a cationic catalyst at temperatures from about C. to about 250 C. as disclosed in a copending U.S. patent application, Ser. No. 382,343, filed July 13, 1964 by M. H. Litt et al. The monomers utilized in this invention may be prepared by conventional means or according to the procedures described in copending US. applications 382,342 and 382,350. The aforementioned applications of Ser. Nos. 382,343 and 382,350 are now US. Patents 3,483,141 of Dec. 9, 1969, and 3,293,245 of Dec. 20, 1966, respectively.

Suitable illustrative monomers of the type represented by Formula I include 2-Inethyl-, 2-ethyl-, 2-cyano-, 2- cyanomethyl-, 2-cyanoethyl-, 2-dimethylamido-, Z-dimethylamidopropyl-, 2 (B carbomethoxyethyl)-, Z-(y-carboethoxypropyl)-, 2 (carbomethoxymethyl)-, 2 acetoxy- 4 ethyl-, 2-butyroXymethyl-, and 2-acetoxymethyl-2-oxazoline, and the like and mixtures of these.

Suitable illustrative comonomers of the type represented by Formula II include 2-propyl-, 2-isopropyl-, 2-heptyl-, 2- undecyl-, 2-dodecyl-, 2-pentadecyl-, 2-heptadecyl-, and 2- octadecyl-, 2-clecenyl-, and Z-heptadecenyl-Z-oxazoline, and the like, and mixtures thereof. In addition, the comonomers may be substituted with functional groups which will not interfere with the polymerization, including chlorine atoms, tetramethyl-ammonium ions, ester groups and the like.

The polymerization temperature range preferred is from about C. up to about 250 C. Polymerization reaction times for preparing homopolymers or copolymers may vary from a few minutes to 12 or more hours, depending on the reactants, the temperature of polymerization, type of catalyst and its concentration, and the desired molecular weight. In general, lowering the temperature of polymerization and/or increasing the time of polymerization and purity of monomers increases the viscosity of the resultant polymer or copolymer for a given monomer to catalyst ratio.

Illustrative cationic catalysts which may be employed for the polymerization reactions include alkyl halides such as methyl iodide and 1,4-dibromobutane; boron-fluorine compounds such as boron trifluoride etherate; antimonyfluorine compounds such as antimony pentafluoride; strong acids such as p-toluene sulfonic acid, sulfuric acid, nitric acid, perchloric acid, hydrobromic acid and hydriodic acid; esters of strong acids such as dimethyl sulfate, methyl sulfate, methyl-p-toluene sulfonate; and salts of strong acids with oxazines such as the reaction product of 2-phenyl-2-oxazine with perchloric acid and the perchlorate salt of Z-(p-chlorophenyl)-2-oxazoline. In general it is preferred to employ a molar ratio of about 10 to 60,000 mols of monomer per mol of catalyst, although alternate quantities may be used. It will be understood that increasing the catalyst concentration will tend to lower the viscosity of the resultant polymers and copolymers.

As a general rule, polymers having a reduced viscosity of from about 0.5 to about 5.0, as determined at 25 C. with a 0.52% solution of polymer in m-cresol and preferably from about 0.9 to about 4.5, are found to be most useful as hair spray resins. Films of polymers of this order have good memory and elasticity; they leave good lustre; they are readily removable by shampooing, and the films will hold a curl or set of the hair even under very warm and humid conditions and tend to resist disarrangement of the hair by wind, contact with objects, etc., very substantially better than untreated hair as well as hair treated with known formulations.

An important advantage of the invention resides also in the fact that a lower concentration of high molecular weight resin in the hair spray formulation is required to deposit a curl-retaining film upon the hair than that required for other known resins and for the lower molecular weight resins. A high resin concentration in a hair dressing formulation is undesirable not only from the economic standpoint but also because in the case of use of the resin in spray formulations a build-up of film deposit will form at the orifice of the spray nozzle of the container, gradually obstructing flow of fluid. Low molecular weight, low viscosity resins have the further disadvantage of being drippy when applied to the hair and tending to dry in a discontinuous uneven fashion.

Hair spray formulations in accordance with the invention may be prepared by dissolving the polymers and copolymers described hereinabove in a suitable solvent, preferably a relatively quick drying solvent such as ethanol, isopropanol, and the like. In spray applications, the solution is then mixed with a propellent prior to packaging. Suitable propellents are known to those skilled in the spray propellent art and include, for example, the fluoromethanes and fluoroethanes such as trichlorofiuoromethane, dichlorodifluoromethane, chlorodifluoromethane, trichlorotrifluoroethane, and dichlorotetrafluoroethane; hydrocarbons such as propane, isobutane and butane; and other volatile solvents such as methylene chloride and 1,1, l-trichloroethane. The fluorocarbons are widely used for a variety of spray applications, but they are not soluble in Water and are not miscible with compounds or solutions containing an appreciable amount of Water, thus, Water must be excluded from hair spray formulations when these propellents are employed.

The resins of the invention can be employed as the sole component in the propellent alone or the solvent-propellent solution, or conventional stabilizers, plasticizers, perfumes, and the like, which are compatible, can be added in the manner recognized by those skilled in the art. Ad-

ditional ingredients for specific purposes can also be used. 1

For example, we have found that a small amount of a glycol modifier will improve the clarity and miscibility of an alkanol solution with other components of the formulation and improves the combabi-lity of hair which has been sprayed.

The amount of each component is not critical and can vary within wide limits. At least about 0.1% by weight of polymer is necessary; lesser amounts require the application of unduly large amounts of solution to be effective. The maximum amount of polymer or copolymer present in the hair dressing composition is generally about by weight. A typical hair spray formulation will contain the film-forming polymer in an amount of from about 0.25 to about 2.0 parts by weight of the formulation, from about to about 70 parts by weight of alcohol, and from about to about 80 parts by weight of propellent. Where desired, plasticizer, modifier and perfume can each be added in an amount from about 0.01 to about 2.0 parts by weight, for example.

Typical illustrative-plasticizers include esters of lanolin alcohols, glyceryl monolaurate, ethylene glycol monobutyl ether laurate, dibutyl phthalate, diethylphthalate and the like. By proper choice of polymer or copolymer, modifier, plasticizer and their concentration, the characteristics and properties of the final formulation can be varied to produce very soft films for easy to set hair or stronger films for hard to hold hair.

The following examples are given to further illustrate the invention. Various modifications will be apparent to one skilled in the art and it is not intended that this invention be limited to the details in the specific examples presented by of illustration. Accordingly, the scope of the invention is limited only by the appended claims. All parts are parts by Weight unless otherwise expressly recited.

Reduced viscosity of the polymers of the examples were determined using a 0.52% by weight solution of polymer in m-cresol at 25 C.

EXAMPLE 1 0.1 mol of freshly distilled 2-decenyl-2-oxazoline, 0.9 mol of freshly distilled 2-methyl-2-oxazoline and 60 grams of N-methyl pyrrolidone were mixed in a polymerization tube. Dimethyl sulfate catalyst was added at a mol ratio of monomer to catalyst of 1000:1. The tube was sealed under a vacuum and heated for 22 hours at 95 C., then at 113 C. for 24 hours, and the polymerization completed by heating at 150 C. for an additional 66 hours. The resultant product was dissolved in chloroform, precipitated by adding excess diethyl ether and dried overnight at 65 C. The copolymer product had a reduced viscosity of 0.96.

A portion of the copolymer was dissolved in methanol. A film cast from this solution was clear, glossy, transparent, non-tacky and flexible.

One part of the copolymer was dissolved in 14 parts of ethanol. parts of this solution was admixed with 65 parts of a propellent mixture containing 65 parts of trichlorofluoromethane and 35 parts of dichlorodifluoromethane. The mixture was charged into a spray container.

The formulation was sprayed onto a glass panel. It

6 dried rapidly to a clear, hard, smooth non-tacky but flexible film. The formulation had good holding power when sprayed on the hair and was easily removed by shampoo- EXAMPLE 2 An acetonitrile solution containing 7.5 10 mol of 2 (p-chlorophenyl)-A -oxazolonium perchlorate catalyst was added to a flask and the solvent removed under vacuum. 0.072 mol of 2-undecyl-2-oxazoline was distilled directly into the fiask,'then 178.5 grams of 'y-butyrolactone added and finally 1.418 mols of dry 2-methyl-2-oxazoline. The mol ratio of total monomer to catalyst was 1984: 1.

The solution wassealed under vacuum and heated in an oil bath at C. for 24 hours. The resultant product was dissolved in chloroform and precipitated with an excess of ether. The product was purified by reprecipitating and drying in an even to a white powder-like solid. A yield of 83% by weight of a copolymer containing 95.2 mol percent of poly(Nethylene acetamide) and 4.8 mol percent of poly(N-ethylene dodecanoamide) was obtained.

The above experiment was repeated at a monomer-tocatalyst mol ratio of 206021 using 1.295 mols of 2-methyl-2-oxazoline and 0.147 mol of 2-undecyl-2-oxazoline. A copolymer containing 90.0 mol percent of poly(N-ethylene dodecanoamide) was obtained.

A copolymer was obtained containing 85.1 mol percent of poly(N-ethylene acetamide) and 14.9 mol percent of poly(N-ethylene dodecanoamide) by polymerizing 1.060 mols of 2-methyl-2-oxazoline and 0.185 mol of 2undecyl-2-oxazol-ine at a monomer-to-catalyst mol ratio of 2075 :1 in a manner similar to that given above.

One part of each of the resins as prepared above was dissolved in 14 parts of anhydrous denatured ethanol, admixed with a propellent and charged into a spray container as in Example 1. The solutions were clear and all formed clear flexible films when cast on glass plates. The solubility of the resins in water decreased as the poly(N-ethylene acetamide) content decreased.

EXAMPLE 3 2.50 mols of 2-methyl-2-oxazoline were dissolved in y-butyrolactone, 2 (p chlorophenyl) A -oxazolonium perchlorate catalyst was'added so that the monomer to catalyst mol ratio was 37 10:1, the mixture poured into a polymerization tube, sealed and heated at 130 C. for 16 hours. The polymer was purified and dried. It had a reduced viscosity of 0.74.

The polymer was formulated to a hair spray as in Example 2 and sprayed onto a glass panel. The film dried in 2.5 minutes to a clear, soft, flexible but pressure-sensitive film. It had good adhesion to the hair.

EXAMPLE 4 2.438 mols of freshly distilled 2-ethyl-2-oxazoline, 0.0333 mol of 2-heptadecyl-2-oxazoline and 5.589 10- mol of ethylene glycol ditosylate as catalyst were added to a polymerization reactor and heated at C. for 17 hours. The monomer-to-catalyst mol ratio was 4400: 1.

Two grams of polymer were dissolved in 68 grams of ethanol and a propellent added as in Example 1. The mixture was charged to a spray container which delivered 4.9 grams of the mixture in 5 seconds.

A film of the copolymer was cast by spraying a glass plate for 5 seconds in a uniform pattern. The film dried in 2.5 minutes to a clear, flexible and non-tacky film.

The mixture was tested for curl retention power on European virgin hair, that is, hair which had not been bleached or dyed, according to the following test: a swatch of hair 17 inches long, tied in the center, was sprayed for 5 seconds on each side and an additional 5 seconds while turning the swatch continuously. The hair was wound on a one-inch roller, removed as a spiral roll and fastened with a hair clip. The curl was dried for 7 minutes at 80 F., kept at 72 F. and 30% relative humidity for 7 minutes and the hair clip removed. The length of the curl was noted. The curl was then hung in a chamber at 95 F. and 100% relative humidity for 5 minutes and measured again. The difference in length is the curl loss.

The curl loss for the hair spray formulation as prepared above was 2.5 inches.

The test was repeated with a control of a commercially prepared resin of poly(vinyl acetate-crotonic acid) resin partially neutralized with amino methyl propane diol, modified by the addition of esterified lanolin, plasticizer and additives. The curl loss was 4.0 inches.

EXAMPLE '5 A series of copolymers was prepared from 2-methyl- 2-oxazoline and 2-heptadecyl-2-oxazoline using 1,6-hexamethylene-d iol ditosylate as catalyst by heating at 150 C. for 24 hours. The copolymer products were purified and dried and formulated as a hair spray as in Example 2. The resins formed clear, bright, flexible and non-tacky films. Curl loss and drying time were determined as in Example 4. The preparation of the copolymers and data are summarized in the table below:

I Monomer: Drying Curl 2-heptadecylQ-oxazolme, catalyst, Reduced time, less, mol percent mol ratio viscosity min inches EXAMPLE 6 A series of copolymers was prepared from 2-ethyl-2- oxazoline and Z-heptadecyl-Z-oxazoline using 1,6-hexamethylenediol ditosylate as catalyst by heating at 130 C. for about 18-20 hours and then at 145 C. for about 12 hours. Hair spray formulations were prepared as in Example 2. Drying time and curl loss were tested as in Example 4. The data are summarized in the table below:

8 EXAMPLE 7 The copolymer as prepared in Example 4 was formulated as given below:

Component: Parts by weight Copolymer 0.56 Isopropylan No. 50 (an ester of lanolin alcohol sold by Robinson Wagner Co.) 0.75 Perfume 0.56 Anhydrous alcohol 36.809

EXAMPLE 8 A series of polymers was prepared from 2-ethyl-2- oxazoline under varying reaction conditions to obtain polymers having different v-iscosities. The polymers were formulated as given below:

Percent by weight Component:

'Poly(N-ethylene propionamide) -Q Acetulan (an ester of a lanolin alcohol sold by American Cholesterol Products Co.) 0.1 Perfume 0.1 Polypropylene glycol 0.2 Denatured ethanol 98.1

37.5 parts by Weight of the above solution were mixed with 62.5 parts by weight of the propellent mixture of Example 1 and charged to a spray container.

The product was sprayed on hair which was rolled and Monomer: Drying Curl dried as in Example 4. The unfastened curlswere exposed 2-heptadecy1-2-oxazoline, catalyst, Reduced time, less, m an at 73 F. and 58% relative humldity for one moi percent moi ratio viscosity min. inches hour v$i g-g g All the resins had good holding power. Those resins 2146021 2:80 2. '25 2:6 having a molecular weight corresponding to a reduced g'gggfi 3 2 viscosity below about 3.0 were slightly pressure sensi- 119101 2. 11 a. 0 1. 8 tive.

o ritfol (see Example 4) -31? 1'5 The preparation of the polymers and curi loss data are summarized in the table below:

Monomer: Curl catalyst, Temp., Time, Reduced loss,

Catalyst mol ratio 0. hrs. viscosity inches 1 col ditosylate 2,780 150 18 1.08 1.1

ib gl iff 3,120 5% g 2. 1. 5

D0 2,520 lgo 6 as 6 P ntaerythritoltetratosylate 7,570 kg 2 "4:5 "5:5

EXAMPLE 9 All of the copolymers formed clear, bright, flexible films when sprayed on a glass plate. When sprayed on the hair, they were found to give a quality of lubricity, or slip, to the hair strands which improves the combability of the curls over untreated hair.

Copolymers prepared from 2-ethyl-2-oxazoline and 2- heptadecyl-Z-oxazoline of varying reduced viscosities were formulated as in Example 8, except that for some the alcohol solution contained 0.1% polypropylene glycol and 0.1% propylene glycol, as identified below. The curl loss test was conducted as in Example 8. The data are summarized in the table below.

Monomer: Curl 2-heptadceyl-2- catalyst, Temp, Time, Reduced loss, oxazoline, moi percent Catalyst moi ratio 0. hrs. viscosity inches 1.60 1 Ethylene glycol ditosylate 4, 080 fig i "5:; n"; 200 1 1,6-hexamethylenedioi 2, 460 20 2. 8 1. 3

ditosylate. 1.57 1 .do 3, 690 130 20 3. 63 1. 4 1.02 do 5, 130 20 4. 46

l Formulation contained mixture of glycols.

9 {EXAMPLE 10 A non-spray hair dressing formulation which may be applied directly to the hair by means of a comb or by hand was prepared as follows:

Component: Parts by weight Poly(N-ethylene propionamide) 20% solution It had a soft supple feel on the ttingers and held a mans hair in place without being noticeable.

We claim:

1. A method of treating hair which comprises applying to hair an effective amount of a hair dressing formulation containing (a) from about 0.1 to about 10 weight percent of a Water-dispersible polymer having a reduced viscosity ranging from about 0.5 to about 5.0 as determined on a 0.52 weight percent solution of polymer in metacresol at 25 C., said polymer being selected from the group consisting of polymers of monomers of the formula N-CH R-O O-CH2 wherein R is a substituent from the group consisting of ll s, C2H5. u 2u-H 2) k-. Cn 2n+10 2)mwherein the sum of the integers m and n is not greater than 6, and

l CN(CH2)1 and s)2N( 3(CH2)k wherein k is O to 3; and copolymers of said monomers with from about 50 to about 0.1 mol percent of at least one comonomer of the formula N-OHZ O-CHz wherein R is a substituent of the formula C I-I or C H wherein y is from 3 to 21; and

(b) a carrier for said polymer selected from the group consisting of water, ethanol, isopropanol, waterethanol mixtures and water-isopropanol mixtures.

2. A method in accordance with claim 1 wherein said R substituent is methyl or ethyl.

3. A method in accordance with claim 1 wherein said comonomer is present in said formulation in an amount ranging from about 0.5 to about 15 mol percent.

4. A method in accordance with claim 1 wherein said comonomer is 2 heptadecyl-Z-oxazoline, 2-undecyl-2- oxazoline or 2-decenyl-2-oxazoline.

5. A method in accordance with claim 1 wherein said polymer is poly(N-ethyleneacetamide).

6. A method in accordance with claim 1 wherein said polymer is poly(N-ethylenepropionamide).

7. A method of treating hair which comprises spraying the hair an effective amount of a hair dressing formulation in a spray container containing.

(a) from about 0.1 to about 10 weight percent of a water-dispersible polymer having a reduced viscosity ranging from about 0.5 to about 5.0 as determined on a 0.52 weight percent solution of polymer in metacresol at 25 C., said polymer being selected from the group consisting of polymers of monomers of the formula /NCH2 RC OCH2 wherein R is a substituent from the group consisting of r r CHz, C2 a, n 2n-HC O 2)m n 2n+1O C(CH2)m wherein the sum of the integers m and n is not greater than 6, and

i CN(OHz)k-, and (CH3)2NO(CH2) k wherein k is 0 to 3; and copolymers of said monomers with from about 50 to about 0.1 mol percent of at least one comonomer of the formula NCl-Iz Rr-O N-CH;

wherein R is a substituent of the formula C H or C H wherein y is from 3 to 21;

(b) a carrier for said polymer selected from the group consisting of water, ethanol, isopropanol, waterethanol mixtures and water-isopropanol mixtures, and

(c) a propellant for said polymer selected from the group consisting of fluoromethanes, fluoroethanes, propane, butane, isobutane, methylene chloride, and 1,1,1-trichloroethane; with the proviso that when said propellant is a fiuoromethane or a fluoroethane said carrier is ethanol or isopropanol.

8. A method in accordance with claim 7 wherein said formulation contains from about 0.25 to about 2.0 parts by weight of said polymer.

9. A method in accordance with claim 7 wherein said polymer is the polymer of claim 2.

References Cited UNITED STATES PATENTS 3,212,972 10/1965 Bailey 42447 3,285,819 11/1966 Blance et al 42471X FOREIGN PATENTS 666,828 11/1965 Belgium 260--2 1,206,585 12/1965 Germany 260-2 STANLEY I. FRIEDMAN, Primary Examiner V. C. CLARKE, Assistant Examiner U.S. c1. X.R. 

